Electrochemical impedance spectroscopic EIS and Mott–Schottky M–S methods were used to determine the density and mobility of charge carriers in the passive oxide layer to understand the
Trang 1N A N O E X P R E S S
The Nature of Surface Oxides on Corrosion-Resistant Nickel Alloy
Covered by Alkaline Water
Jiaying Cai•D F Gervasio
Received: 16 November 2009 / Accepted: 17 December 2009 / Published online: 5 January 2010
Ó The Author(s) 2010 This article is published with open access at Springerlink.com
Abstract A nickel alloy with high chrome and
molyb-denum content was found to form a highly resistive and
passive oxide layer The donor density and mobility of ions
in the oxide layer has been determined as a function of the
electrical potential when alkaline water layers are on the
alloy surface in order to account for the relative inertness of
the nickel alloy in corrosive environments
Keywords EIS Mott–Schottky Bipolar plates
High-temperature PEM fuel cell Nickel alloy
Introduction
Nickel metal alloys are corrosion resistant and can serve
as structural materials in extraordinary environments, e.g.,
in long-term storage containers, high-temperature heat
exchangers and aggressive chemical reactors The stability
is often attributed to the inertness of the oxides that form on
the nickel alloys One new application of these
extraordi-nary alloys is as the structural material for a metal bipolar
plate in a polymer electrolyte membrane (PEM) fuel cell
stack
The bipolar plate is among the most expensive, heaviest
and voluminous components in the fuel cell stack The
bipolar plates conduct current between cells, provide flow
channels for reactants and products, facilitate water and
thermal management and constitute the structural backbone
of a fuel cell stack The materials for bipolar plates need to have high electric and thermal conductivity, good corrosion resistance and mechanical strength Replacing bulky, brit-tle machined graphite plates by thin, durable stamped metal plates is particularly desirable for portable and mobile applications where lower bulk, fragility and cost are all needed
After an earlier accelerated corrosion screening test [1], the high chrome molybdenum nickel alloys, such as Hastelloy C22 (composition given in Table1), were con-sidered one of the few materials with structural stability that is suitable for use in bipolar plates for a high-tem-perature PEM fuel cell stack
Compared with graphite, C22 can be made into bipolar plates from much thinner sheets The thickness of a C22 metal sheet is \0.1 mm, whereas that of a graphite sheet is [2–5 mm The C22 can be formed into a bipolar plate by a lower cost stamping as the manufacturing method, which costs only 10 cents to $1 per plate when compared to $5–$25 per plate for the milling or molding a graphite plate [2] These features of metal bipolar plates are desirable for making a more compact, lighter weight and lower cost fuel cell stack
Most importantly, alloy C22 shows remarkable corro-sion resistance and stability that is suitable in the aggres-sive fuel cell environment A number of studies on its general and local corrosion resistance suggest that C22 has excellent resistivity in a broad range of concentrated brines including chloride, fluoride, carbonate, sodium and calcium over a large pH and temperature range [3] It is mainly due
to the formation of a protective passive oxide layer on the surface This occurs through electrochemical ‘‘local cell’’
on the metal surface, where oxygen reduction occurs at one localized metal surface site by accepting electrons
J Cai (&)
Department of Chemical Engineering, Arizona State University,
Tempe, AZ, USA
e-mail: jiaying.cai@asu.edu
D F Gervasio
Department of Chemical Engineering, University of Arizona,
Tucson, AZ, USA
DOI 10.1007/s11671-009-9521-5
Trang 2generated during metal oxidation occurring at another
localized site through electron conduction in the bulk metal
[4] The oxygen reduction site becomes alkaline, and metal
oxidation site becomes acidic Nickel alloy was placed in
aqueous potassium hydroxide solution and exposed to
various oxidizing potentials representative of a bipolar
plate at an oxygen cathode Electrochemical impedance
spectroscopic (EIS) and Mott–Schottky (M–S) methods
were used to determine the density and mobility of charge
carriers in the passive oxide layer to understand the nature
of the surface oxides and how these affect the corrosion
resistance of C22 nickel alloy covered by alkaline water
Experimental
Electrochemical Measurements
All electrochemical experiments were carried out using a
three-electrode configuration at room temperature The
working electrode was nickel alloy C22 (Haynes),
machined into 6 cm 9 2 cm 9 0.2 cm The working
electrode was abraded with 1200-grit SiC paper, polished
with 1.0, 0.3 and 0.05 lm Al2O3powder and then
ultra-sonically cleaned in deionized water The working
elec-trode area was 12 cm2 A Ag/Ag2O reference electrode was
used in 0.1 M KOH (pH 13.0) and in 1.0 M KOH (pH
13.8) electrolyte solution The potential of the
silver/silver-oxide reference electrode is 0.321 V versus RHE in 0.1 M
KOH and 0.341 V versus RHE in 1.0 M KOH This can
be related to NHE (pH = 0) by the potential shift with
pH using the Nernst equation A graphite rod was used
as the counter electrode The aqueous alkaline potassium
hydroxide solutions of two concentrations (0.1 M, pH 13.0
and 1.0 M, pH 13.8) were prepared using pure deionized
water (PureLab Ultra system) and potassium hydroxide
stock (analytical-grade reagent) The solution was
deaer-ated with ultrapure nitrogen gas for 30 min prior to starting
the experiment, and this nitrogen purge was continued
throughout each experiment Voltammetry of Alloy C22
was performed to determine the electrochemical processes
that occur on the moisture-covered alloy surface After
freshly abrading the C22 working electrode, it was
cathodically polarized at -1.3 V for at least 20 min to
remove the air-formed oxide film, then the potential was
swept from -1.3 to 0.5 V at a scan rate of 20 mV/s to
survey the surface processes The C22-alloy working
electrode was held for 2 h at each film formation potential
to grow the passive oxide films
EIS and M–S tests were carried out immediately after the passive films were formed For EIS measurements, the fre-quency was analyzed over a range of 10 kHz–1 MHz with a peak-to-peak modulation amplitude voltage of 20 mV And then, the M–S experiments were done by measuring the frequency at 1 kHz during a negative potential scan from
?0.2 to -1.1 V in 50 mV-increments
All electrochemical experiments were performed using a Princeton Applied Research VMP2/Z Multichannel Poten-tiostat (Oak Ridge, TN) running EC-Lab version 9.13 soft-ware, and the impedance spectra analyses were performed using Zsimpwin software
Interfacial Contact Resistance (ICR) ICR should be minimized for bipolar plates to achieve high efficiency in PEM fuel cells ICR measurement was con-ducted on the Hastelloy C22 after the electrochemical oxidization The apparatus for measuring ICR is illustrated
in Fig.1, showing two pieces of carbon paper (SIGRACET, type GDL 10 AA, a gas diffusion layer used in PEM fuel cells) sandwiched between the sample and two copper plates Compaction force was applied by a hydraulic press The potential difference V across the cell and the copper plates was measured by an ohmmeter while a fixed elec-trical current I (0.9 A) was passed through the arrangement The ICR was calculated as follows [5]:
ICR¼R Rcp
Copper plate
Copper plate
Carbon paper
Carbon paper
Fig 1 Apparatus used to measure interfacial contact resistance
Table 1 Chemical composition (wt%) of Alloy C22
Trang 3where R is the total resistance (V/I), Rcp represents the
resistant contribution due to the carbon paper/copper plates
(*5 mX) and A is the sample area (cm2) The value of ICR
was greatly affected by the compaction force, and good
reproducibility could be obtained only with compaction
force above 200 N cm-2[5,6]
Auger Electron Spectroscopy (AES)
In order to determine the general composition of
surface-oxidized C22, AES was performed to get depth profile for
oxidized samples AES analyses were carried out on
speci-mens at sputter rate of 2.0 nm per minute with beam current
of 1.0 lA and beam voltage of 4.0 kV using Physical
Electronics 590 Scanning Auger Microprobe
Results and Discussion
Cyclic Voltammetry
The cyclic voltammogram presented in Fig.2 shows the
surface processes occurring on alloy C22 in both 0.1 M
(pH 13.0) and 1.0 M KOH (pH 13.8) solution Figure2
shows that the first cycle was noticeably different than the
successive cycles The first positive-going sweep shows
extra anodic current from -0.7 to 0.3 V, suggesting the
formation of a metal oxide layer on the alloy C22 surface
The reverse scan showed the reduction peak between 0.1
and 0.3 V in the first and succeeding negative-going scans
The second and successive positive- and negative-going
scans showed growing oxidation and reduction peaks
After the third cycle, the growth rate of both oxidation
and reduction peaks decreased and were virtually
sta-ble Figure2b shows a similar behavior for the cyclic
voltammogram of the C22 in 1.0 M KOH, except there are two noticeable differences First, there is a slight shift for the anodic peak, which was 0.3 V (vs Ag/Ag2O/0.1 M KOH) for 0.1 M KOH and 0.26 V (vs Ag/Ag2O/1.0 M KOH) for 1.0 M KOH solutions Secondly, both the oxi-dation and reduction peak currents were about two times larger in the solution with 1 M versus 0.1 M KOH Interfacial Contact Resistance (ICR)
Figure3shows the comparison of the ICR of the alloy oxi-dized at different potentials in both 1.0 M KOH (pH 13.8) and 0.1 M KOH (pH 13.0) solutions The results showed that the alloy oxidized in 0.1 M KOH had a higher ICR value than that in 1.0 M KOH solution In both solutions, the ICR values were higher in the passive region (-0.5 to -0.1 V) and decreased at the higher potential conditions
Generally, the influence of Cr-oxide on the Ni-based material resistance is very complex, and it can be considered
-10
-5
0
5
10
15
E (volt) vs Ag/Ag
2
1st scan
2 nd scan 3rd scan
-10 -5 0 5 10 15
1st scan 2nd scan
3 rd scan
O in 0.1M KOH
Fig 2 a, b CV of C22 in 0.1 M and 1.0 M KOH
32 34 36 38 40 42
Fig 3 Interfacial contact resistance of alloy C22 after oxidized at -0.5, -0.1, 0.1 and 0.2 V in 1.0 and 0.1-M KOH solutions
Trang 4that the decrease of conductivity follows the trend that the
conductivity of Ni-oxide is greater than the conductivity of
Cr-oxide [5] Therefore, it appears that when alloy C22 is
oxidized in 0.1 M KOH solution, a larger amount of
Cr-oxide forms on the surface, which results in a higher value of
ICR The depth profile for the oxide films on C22 by AES
(not shown here) showed more Cr-oxide was formed in
0.1 M KOH, which is consistent with this assertion
Impedance Measurement
EIS and M–S tests were carried out on the passive films
formed at different potentials in order to investigate the
influence of the film formation potential on the character of
passive films on alloy C22 The Nyquist plots are shown in
Fig.4a and c for the nickel alloy in 1.0 and 0.1 M KOH
electrolyte The impedance data can be modeled by a
simple equivalent circuit Rs (CscRp), where Rs is the
electrolyte solution resistance, Csc is the space charge
capacity and Rp is the polarization resistance It is clear
that the impedance response is sensitive to the film
for-mation potential In both 0.1- and 1-M KOH solutions,
smaller arcs were observed in the potential range of 0.2 and
0.4 V, while larger ascending arcs, which do not form
semicircles on the real axis, are observed between -0.3
and -0.1 V This phenomenon is more clearly shown in
Fig.4b and d, where Rp initially increased with potentials
(within the passive range), but when potentials are within the trans-passive region (E [ -0.1 V), Rp decreases with
E The existence of the resistance Rp versus E peak can be attributed to the establishment of passive oxide layer in the beginning and then the oxidative ejection of chromium cations from the barrier oxide layer [7]
The impedance behavior for alloy C22 in the 0.1- and 1-M KOH solutions show one systematic difference, namely, the arcs are always larger in 0.1 M KOH It appears that the higher concentration of [OH]-ions results
in a less-resistive passive oxide film on the nickel alloy surface, especially in the potential range between -0.5 and -0.1 V The possible formation process of metal oxide is presented as follows
M! Mxþþ ex
½OHþ Mxþ! M½OHx! MOx=2
Having more [OH]- ions in solution favors the above reaction, and hence, the quick formation of an passive oxide layer, which covers the metal surface and slowed down the further oxidization of metal
Following each EIS measurement, an M–S test was performed to study the semiconducting properties of a passive oxide film that was formed on the surface of the nickel alloy The M–S analysis measures the electrode capacitance as a function of potential Under depletion conditions, the M–S relationship is given by Eq (1)
0 5000 10000 15000 20000 25000
0 10000 20000 30000 40000 50000
in 1.0 M KOH
0 10 20 30 40 50 60
Potential (V)
0 50000 100000 150000
0 20000 40000 60000 80000 100000
in 0.1M KOH (pH 13.0)
0 50 100 150 200 250 300 350
E (V)
Fig 4 a, b EIS of C22 in 1.0 M KOH c, d EIS of C22 in 0.1 M KOH
Trang 5C2
SC
eee0NA2 VE VfbkT
e
ð1Þ
where CSCis the space charge capacitance, e is the dielectric
constant of the semiconductor, e0 is permittivity of free
space (8.854e-14F/cm), N is defect density (electron donor
concentration for n-type semiconductor or hole acceptor
concentration for p-type semiconductor) and k is the
Boltzmann constant kT/e is the thermal voltage, which is the
voltage a single charge falls through to pick up the thermal
energy kT/e is about 25 mV at the ambient temperature
The M–S analysis assumes the space charge capacitance
is much smaller than the double-layer capacitance such that
the contribution of double-layer capacitance to the total
capacitance value could be negligible For a p-type
semi-conductor, C2SC versus E should be linear with a negative
slope, which is inversely proportional to the acceptor
density N For an n-type semiconductor, the slope should
be positive
Figure5 shows the M–S plots recorded at 1 kHz
fre-quency for passive films formed on Alloy C22 in 1.0- and
0.1-M KOH solutions at different potentials
As shown in Fig.5b, the capacitance decreased (CSC2
increased) at low potentials (-1.1 \ E \ -0.8 V),
sug-gesting an n-type semiconductor At higher potentials
(E [ -0.1 V), however, the capacitance increased (C2SC decreased), showing a p-type semiconductor The change
of the electronic character is more likely due to the gen-eration of the cation vacancies at film/solution interface through the oxidative ejection of cations from the film [8] This result is consistent with the above Nyquist plots where the most resistant film was formed at the potential of -0.1 V, where the change of electronic character appeared Over the potential range between -0.8 and -0.1 V, the capacitance was nearly constant, for those passive films formed at lower potentials (-0.5, -0.3, -0.2, -0.1 and 0.1 V) This phenomenon was also reported by Da Belo
et al [9] on Ni-20% Cr alloy in pH 9.2 borate buffer For those passive films formed at higher potentials (0.2, 0.26 and 0.34 V), there was no clear potential range over which the capacitance varies slightly Their M–S profiles behaved similar to those of the films on pure Cr, which presents a peak in the C2SCversus E plots followed by a steadily linear region negative slope (see [10])
Defect density N of the passive films could also be determined by the slope of the linear part of M–S profile Both the donor density calculated from the n-type part and the acceptor density from the p-type part in passive films formed in 1.0-M KOH electrolyte solution are larger than those formed in 0.1-M KOH solution (see Fig.6) The
0.0E+00 5.0E-05 1.0E-04
E (volt) vs Ag/Ag 2 O in 0.1 M KOH
-2 (F
-2 )
-0.5 V -0.1 V 0.3 V 0.35 V
0.E+00 5.E-05 1.E-04
E (volt) vs Ag/Ag 2 O in 1 M KOH
-2 (F
-2 )
-0.5 V -0.2 V 0.26 V 0.34 V
(b) (a)
Fig 5 a, b M–S test of C22 in
1.0 and 0.1 M KOH
n type
0 5 10 15 20 25
Potential (volt) vs Ag/Ag 2 O
-3 ) x
p type
0 5 10 15 20 25
Potential (volt) vs Ag/ Ag 2 O
r ( cm
-3 )
Fig 6 a, b Donor density
(acceptor density) versus film
formation potentials
Trang 6higher defects concentration within the film resulted in
lower resistant passive films, and accordingly, higher
conductivity, which was in a good agreement with the ICR
and Nyquist results
AES Depth Profile
Figure7 showed the content of three major components
within the surface oxide films on alloy C22 versus the
depth of the films
In all cases, the amount of Cr-oxide was slightly higher
in 0.1-M KOH than that in 1.0-M KOH solution This
result is consistent with the effect of solution pH on the
ICR value, which was higher for the oxide films formed in
0.1 M KOH
The depth profile (b) behaved quite different from the
other two cases For the oxide film formed at -0.1 V, the
content of Cr-oxide is higher in the outer layer of the film,
which was *51% formed in 1.0 M KOH and *55% in
0.1 M KOH compared with *20% in the bulk alloy It
decreased greatly from the outer to inner surface at the
depth of 2 nm, while the content of Ni-oxide increased and
finally dominated in the inner layer of the film However,
for the oxide films formed at -0.5 and 0.26 V, this
dual-layered structure was not observed And the Ni-oxides
were dominant through the entire oxide film This result
could also be explained the highest value of ICR for the
oxide film formed at -0.1 V, which the higher amount of
Cr-oxide was responsible for the higher contact resistance
The thickness of the oxide films was estimated by the depth
profile at the range of 3–4 nm, where the three components
Cr, Ni and Mo converged to a state value, respectively
Conclusions
The oxide film that forms on nickel alloy C22 is affected by
film formation potential and pH ICR and EIS show the
interfacial film resistance Rp is sensitive to the film
for-mation potential The current for the forfor-mation of oxide
peaks at the potential of -0.1 V More concentrated KOH
electrolyte solution contributes to the formation of less
resistant and hence larger peak current for this passive film
formation at 0.1 V on nickel alloy C22 The M–S analysis
of the oxide layer on nickel alloy C22 shows that the oxide
film on the nickel alloy is semiconducting when formed in
both 0.1- and 1-M KOH solutions Over lower potential
range, the oxide film on nickel alloy C22 displays n-type
character, while p-type character is found at higher
potentials Defect concentration obtained from the M–S
plots is higher when the film is formed in 1.0-M KOH
solution at all the investigated film formation potentials,
which is consistent with a lower film resistance for oxides
formed in 1-M compared to 0.1-M KOH solution The AES depth profile shows a dual-layered structure in the oxide film formed at -0.1 V, where a Cr-rich outer layer is responsible for the higher contact resistance The amount
0 10 20 30 40 50 60
depth (nm)
(a)
0 10 20 30 40 50 60
depth (nm)
(b)
0 10 20 30 40 50 60
depth (nm)
(c)
Fig 7 AES depth profile of the oxide film on alloy C22 formed at -0.5 V (a), -0.1 V (b) and 0.26 V (c) in 0.1 and 1.0 M KOH
Trang 7of Cr showed in the depth profile was higher in 0.1-M KOH
than that in 1.0-M KOH solution, which further confirmed
that a more resistive oxide film grows on the nickel alloy
when it is covered by a less concentrated aqueous KOH
(less basic) solution
As is, this alloy is stable enough to be used as a bipolar
plate in a high-temperature polymer electrolyte membrane
fuel cell (HT PEM FC), but the surface conductance of this
alloy is too low to be used as a bipolar However, coating
with a thin stable conductive layer, such as gold, will give
suitable surface conductivity Because the Hastelloy C22 is
inert to corrosion, defect in the gold coating will not grow,
and a gold-coated Hastelloy C22 bipolar plate should be
suitable for use in a HT PEM fuel cell Ongoing work
concerns testing this assertion in HT PEM fuel cell stacks
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